Oxidation catalyst for hydrocarbon combustion exhaust gases and process for using the same



w. B. INNES A ril -15, 1969 3,438,72l DROCARBON COMBUSTON ExH GASES AND PROCESS FOR USNG THE SAME AUST OXIDATTON cATALYS'' FOR HY or1gina1 Filed Dec. 1o 1964 ooooopooo oo ooooooo oooooooooo oooooooooo ooooooo oooooooooooo oooooooooo ooooooooo ooo 0ooooooooo oooooooooooo oooooooooo oopoooooooooo uoooqooooo oooooooooooo ooooooooooo ooooooooooo ooooooooooo oooooooooooo oooooooo o ooooooo oo o oooooo poooooo ooooooooo ooobooooo oooo oooooooo ooooo oooo ooooooo oooo ooo oooo ooooooooo oooo oooooooo the eXhaust-gaS-converer catayst bed S retarded by backpressure, In the discussion of catalysts, the term "par ticle" includes any one or more of typical physical forrns Such aS extrudates, beads, rings, etc AuOmObile engines and exhaust Systems are designed in a manner Whereby there is a particular bllilt-in, inherent back-pressure in the exhaust System` Ihe California standards permit a Tnaximum increase in back-pressure Of ony about 25% above the rigina1 back-pressure The requireInent is now expressed in ternS Of percentage change in horse power( Regardless as to the design of the exhaust converter and aS t0 the shape 0f the catalyst, the ninimum CrOSS Section iS critical in order t0 avoid excessive back-pressure The problem arising from the maximum rmiSSible back-pressure, and thereby from the mininum catalyst particle cross Section, is complicated by a counter'pr0blen1 which limits the n1aximum cross secion, ertainin both to spherica1type and to oblong type, as Well as other Shaped catalysts Although minimum CrOSS Section iS the 0ptimal for reas0ns discussed below, and although a larger particle of a particular catalySt Inay be nece3sary t0 av0id excessive back-pressure in an autom0bile exhaust converter, he eInpyment of large parlicles n]ay result in a channeling 0f exhaust gases caused, for example, by rearrangement of the catalyst bed, Whereby the channeled eX- haust gases escape in0 the at[n0sphere without undergoing conversion, i'e., the converter is rendered ineec ive An0ther probleIn arises from the inherent 0Veral pore Volurne 0f the particular catalyst{ AS the pore v0lume increases, the crush Strength decreases Whereas the activity after eading increases for the conversion 0f exhaust gas hydr0carbons Another problefn arises from the effects Of CrOSS Section of catalyst on the exhaust catalyst resistance to deactivation as a Tesult of leading arising fr0m the 11Se Of leaded fuels AS cross Section of the particles increases, the particle accumulates lead at a lover rate' HOWever, as the cr0ss section increases, leaded activity of the 0veran cat alytic bed decreases for exhaust gaS hydrocarbon conver sion The phen0menon of greater lead accumulation aS cross Section of the particles decreases, resul{s from the iInpingement of the exhaust gas OW upon the catalyst particles making up a catalyst bed. Sn]aller CrOSS Section inherently resl11ts in a n0re c0mpact bed and greater impingement.

Separation of dust or miSt by packed beds iS due t0 Several factors including the f0]lowing;

Separation by impingement is controuing at high gas velocities encountered in exhaust C0nverters. The conection 6Hiciency by impingement is deHned by lhe f01lowing equation:

gravity Settling Brownian Movement impingement interception electrostatic attfaction J =terminal setting ve10city 0f the dust or mist V gas ve10city in the bed.

g =gravitational constant' :dianleter Of the catalyst particle.

ature." The high ignition temperature Of V 0 for ex- 3.IT1)le, results in long initial periods of Warm-UP and n0nconversion 0f gases, thereby resulting in a high degree Of air p0llution ri0r t0 The Obtaining of the igniiOn teInperature 'lhe counter-problem arises ffom the fact that catalyst particles of large CTOSS Section form a less coInpact catalytic bed than iS forlned by catalyst particles Of a small cross Section, When ernp10yed aS a catalytic bed in an auton10bile exhaust converter BecauSe the larger particle catalysts are 1eSS effective for the in1pingement separation of lead aerosols from the exhaust gases, the entire Catalyst bed Tapidly 10Ses a Substantial degree of its activity Whereby the ignition temperature is Substantia]ly Taised thereby permitting large quantities of smog forrning exhaust gases to PaSS into the atn108phere In contrast, the SnTallel Particles, ie', particles having a Small CrOSS Section, form a In0re COInpact (Wa11space) catalytic bed and have greater irnpingement (1) Whereby catayst particles C10SeSt to an exhaust converter inlet conect a Substantial p0ftion of the lead and (Z) Whereby the remainder of the catalytic bed refains a high degree of ac tivity thereby retaining a 10W ignition temperature and preventing uncontr011ed pouution of the atn10sphere 1hus, a Snlall cross section iS necessary in order t0 prolong the eective life and a 10W ignition temperatufe of the cata1ytic bed ()n the other hand, When particle cross secion is de creased, it is concurrenty nece8sary that the catalytic Support in the aut0m0bile exhaust converter have perforati0ns Which are Smaller S0 that the catalyst Will not b6 blovvn through the perf0rations or Will not filter through the peTf0ratiOnS Ihe requirement that these perforations be Smaller than the catalyst particles enp10yed in a catalytic bed Of an automobile exhaust catalyst iS Often ffustrated by the tendency Of the sman perforations TO become plugged, Whereby excessive backpressure Te Sults and vvhereby rupture Of the aut0mobile exhaust converter or channeling of the exhaust gases through the cataytic bed Inay result- Thus, in order to be successfully emp10yed in an aut0- In0bile exhaust converter, the CTOSS Section of the exhaust gas catalyst particles cannot be less than a particular I1initn11n, in contrast to the Severa1 probleIns already diS cussed above relating t0 cr0ss Section of the catalyst' The 0btaining of a Satisfact0ry catalyst is further complicated by the fact that the catalyst iS Subject to varying conditions such aS Starting and Stopping the mot0r, With periods of running a cold motor, and alternatively of periods of extenisve use Where the engine heat is at a high level The problem of overheating is typically illustrated by Table VI' I"BIE vI Potentia1 Tem erature 1.) (ontribution Aut0mobile Sens1)1e Tota1 Hydr0 00+H IIet Temper carbon (Degrees; ature E. E.

Idle 250 800 200 l 250 500 500 150 1, 150 450 600 150 1,200 00 1,100 00 1,900 :l:) 650 350 150 1,150 600 750 1,350 2,600 650 350 200 1,200 900 350 150 l,400 300 500 (:l:) 350 l,200 350 1,100 450 1,900 060- 750 (:l:) 950 (:l:) l 800 Weig al (0al. TOSt)----- 500 550 225 l 325 A catayst retains its activity for the cOnverS0n of exhaust gas hydf0carbons and carbon nlonoxide Only S0 10ng as it is not subjected to continuous excessive ten1- Peratufes resulting from 0verheating The typical exhaust gas c0ntains about 1jZ Water Vapor, and the catalyst bed is, therefore, continuany Subjected to steaming aS WeH as many 0ther assorted reactions ()Verheating accelera[es the 10SS Of catalyst activity Additi0nauy, excessive eX These and other objects and advantages of the present inventin vvill become more apparent fronl the de tailed description thereof set forth hereinbe]0w The app1icant's auton10bile exhaust gas catalytic com- 0Sition, vvhen employed in an aut0n10bile exhaust gas converter, 0btains the above 0bjects For example, the applicant's exhaust gas catalytic C0mp0sition, emp10ying V 0 and a copper c0mpound Slch as copper 0Xide as nec essary c0np0nentS, and preferably additiona11y empying at least one catalyst Selected from the noble me[als (1) 0vercofnes the overheating problem S ecic t0 aut0mobile exhaust gas converters, (2) is characterized by a 10W ignition temperature, thereby requiring only Ininor vvarning up periods, (3) obtains a high percentage conversion of both carbon mon0xide and total hydrocarbons, particular- 1y 0f ethylene and 0lenS Of three or more carbon at0ms, and (4) has a high Stability to both lead p0isoning and t0 Steaming condition3 While concurrent]y being highly active at a Small CrOSS Section of the catalyst partCle' According t0 the present invention, the 0Xidation catalyst c0m rises a rnajor porti0n 0f aluInina, and as catalytic agents, between about 2 and about 10 vanadia and between about 2% and about 10) of copper, Ol Copper compound such as Copper 0Xide, the percentage Of c0ppef being expressed in terms 0f the vveight Of elemental copper Additional]y, it iS advantageous to include from between about O 01% (100 p'm') to about 0 03) (300 p.p m Of paladia, or an equivalent amount Of some other noble metal The noble metal normauy is emp10yed aS a Salt The particular noble metal employed Should be one which Will Inore eifectively catalyze the 0Xidation of hydrogen, carbon mon0xide, ethylene propylene, and higher 0lenic components of the con1bustion exhaust gases at lovv tenperatures, ie., at teInperatures less than about 400 C t0 about 4jo C than the v 0 cataytic component of the catalyst' Thus, according t0 the )Iesent invention, the exhaust gaS converter catalytic com osition includes vanadia and a copper c0mpound, preferably copper 0xide, as essential c0n]ponents, and advantageous1y, includes a minor percentage 0f one 0T In01e such as platinum, pauadium, rhodium, iridium, rutheniun, and 0Sn1ium ()ther c0pper compounds typi cally include either or b0th cupric and cuprous salts of chloride, cyanide, nitrate, ferricyanide, ferr0-cyanide, uOride, Sulfide, sul ite, thiocyanate, acetate carbonate, 0Xides and mixtures there0f.

S discussed above, the utilization of a catalyst in an auton10bile exhaust gas converter raises many Problems not ordinarily encountered in the catalyst art According ly, in order t0 have the required CrLISh Strength, Stability to steaming and to lead p0isoning, permeability to gas How t0 prevent excessive back-pressure, catalytic activity for the conversion of hydr0carbons and carbon Inon0xide, 10W ignition temperature, and other requirements discussed above, it is critica1 that the applicant's catalytic comp0sition have a pore volulne of about o 7 to ab011t 09 cc-/g, and a particle Size having a Ilinin1111 Cr0SS Section of about inch (0.05 inch) 0 about inch (0 20 inch) 1^he catalyst c0np0sitions of thiS invention may be pre pared by impregnating a suitable alumina base with a prescribed amount of V 0 i.e., vanadium pent0xide, fol- 10vved by impregnating With the second catalytically active Inaterials described hereinab0ve' A1ternative1y, the inpregnation Pr0cedure may be reveTsed, i.e the second catalytic Inaterials being the iirst impregnant, f0110wed by impregnation with V 0 A Second and inlportant aspect of the catalyst COIn position of this invention relates to a comp0sition Which iIl essence Inay be described as a physical mixture Of a v 0 impregnated alumina with an alumina base material activated with the second catalytic material This method of preparation and the catalyst con1positions resulting therefr0111 fesult in Substantial iieibility in catalyst COIT1 positions of this invention in that the relative alnounts 0f catalytica11y active c0mponents may be varied quite readily by the si[n1)le addiiion ()I' Subtraction of one of the optional components, Since units for dieTent cars Will Tequire varying amounts of 10W temperature heat release, depending on 10cation of the cataytic unit and exhaust c0mposition, this iiexibility iS important. Additionally Where the catalytica11y active material includes a noble Tetal, by I1Sing physical mixtures 0f the tw0 6SSential catalytic cornponents, the noble Inetal iS I1Ofe easily Tecovered after use, vvhich iS an important economic advantage AS compared With 0 alumina catalyst heretofore used f0r the 0Xidation Of hydr0carbon combustion ex haust gases, the catalyst c0mposition of the il1stant in vention haS Severa1 marked advantages' It results in T10re eeCtive 0Xidation of harmful ethene, ropylene and carbon In0n0xide, in the environn1ent of an automobile ex haust converter' I`he presence Of at least one copper con1- pound and preferably a third catalytic agent, as for ex ample, Platinum, resultS in a Substantial1y faster vvarmup of the catalyst bed in c0mparison With that 0f v 0 aluInina catalyst Faster Warmups of the catalytic bed result principally from the 0xidation Of hydrogen and carbon non0xide by the second catalytic con1ponent which performs more efectively at 10W temperatures than the 0 `alumina portion of the catalyst composition This 0xidation at low temperatures Of the abOveidentied constituents of c0mbustion exhaust gases results in the rapid Telease of heat due t0 the 0xidation of these con- Stituents, vvhich in turn causes the entire catalyst bed t0 Warm llp substantia11y immediately and thereby renders the v 0 -Al 0 C0mponent active f01 hydrocarbon oxidation Thereby applicant's n0vel C0Inposition obtains the desiable low ignition ten1perature Iand0n catalytic C01T1p0sition catalysts of Solely a copper compound Such aS (;u0, and/0r Solely a noble nletal, although very active and highly eective 0Xidation cata lysts for hydrogen and carbon monoxide, are in them- Selves I10t suited for catalytic nlumer usage in the absence of the 0 -aluInina catalytic c0mponent This is true because their use (vvithout vanadia) reqllires the supply Of SLlicient additional 0Xygen to con1pletely react with the carbon mon-0xide and hydr0gen bef0re very effective conversion or 0Xidation of hydrocarbon constituents of the exhaust gases can be Teaized. This means high air or 0Xygen requirenents vvhich in turn means large ca acity air induction devices Which are not always adap table to an automobile exhaust gaS converter system.

Additionally, vhefe high oxygen requirements exist, the heat released fr()m the Tapid and near c0nplete 0xidation Of carbon mon0xide, hydr0gen and to a lesser extent hydrocarbons, fesults in a Tise of the temperature of the catalyst bed t0 very high te[nperatures vvhich can damage the catalyst and the container there0f, aS vvell as affect nearby C0Inponents in an auton10bile or 0ther apparatus emp10ying an intefnal conlbustion engine if the container and exit pipe are l10t Well i11sulated, aS discussed above Further, hot exhaust gases als0 present a Safety problem, Such aS OSsibly causing a fire.

More0ver, catalysts containing noble ITletals (vvithollt 0 as an active catalytic Component have a high Susceptibi1ity t0 lead poisoning ff0m leaded fuels at high temperatures, and as is Well knovvn the noble I11eta Catalysts aTe COInparatively expensive The c0mbination of vanadium pentoxide 0 and a c0pper c0mpound Such as (;l10, preferably vvith at laSt one catalytic noble metal such as palladiun1 or platinun1, With alumina base material in the amounts described has t0 a substantial extent overcome the disadvantages of either a copper compound 01 a noble metal catalyst em- 10yed alone Thus, vvarnup times are Substantially reduced, resulting in a catalyst c0mp03ition that iS eective in very Short periods of tin1e, and a catalyst iS rovided which is effective for ethene (ethylene), as well as higher 15 conTpsiti0ns of dierent cTOSS Secti0ns. The TSt catalyst has a cTOSS Section (diameter) of (a) 0-07 inch, and the second haS a cross section Of (b) 0 049 inch vVhere the cross Section 0(070 represents unity the relative pres- Sure d0p caused by the catalyst of 0.049 inch cross Section is l.46, baSed 011 the formula:

Where:

F=a friction factor E=void v01ume/unitv01ume of bed Z=E+ ore vo1./unit v01(+skeleta1 volume A 0 unit v0l Therefore,

1 E: 1 BD(PP' this is the fornula for the v0id Volume.

It is important that the catalysts be characterized by the physica1 roperties described above in 0rder that a Sub- Stantial I111n1ber of these pellets may be empyed in a given converter unit of SuiCientSiZed cOnguratiOn, While concurrently av0iding the deve10pnlent of significant back pressure in an exhaust systeIn, Which back pressure Would res111t'il1 the din1inishing of 0Wer and eHiciency Of a given engine, and vvhich could cause the automobile exhaust gas converter t0 bec0Ine ineeCtiVe for future conversion of the gases, as discussed above In accordance with the abovementioned alternative n1ethods for preparing the Catalyst n1aterials of this invention, after the impregnation Of a Suitable alumina With vanadium pentox*ide, the material may be pelleted aS in c0nventional peneting or extruSion apparatus and there after dried an calcined If these pellets are not t0 be further impregnated With a copper c0mpound and a noble metal, but are t0 be physica11y blended With a copper compound and a noble Inetal on alumina catalyst nlate metal, but are t0 be physically blended With a copper coTnpound and a noble metal on aluInina catalyst materia1, a Suitable alumina base is impregnated With metauic CI1 01 vvith a copper compound, and preferably alSo With a suit able noble metal salt. The suitable alumina base is prefel' ably in the ultimate physical form of the catalyst, that iS, aS a pellet, bead or othervvise f0rnled base A Suitable noble metal salt may be, for example, ch10roplatinic acid re pared in accordance With the pr0cedure and the art Well deve10ped in the area Of catalysts for the reforming of petroleum hydr0carbons, aS for exaInple, those described in I'S. Patent 2,479,109, IJ.s. Patent 2,840,514 and IJ S. Patent 2,840,SZ7. The disc0sures contained in these pat ents ale typical of prior art deve10ped in the reforming catalytic neld and are incorp0rated herein by reference After impregnation of the alumina base With copper and preferably also with the noble metal, the coppernoble 6 meta1alumina catalytic component is dried 'in accordance vvith Well known procedures such as th0se described in the above referred to pate[1ts and the )ellets are cal- Cined 'lhe Step 0f calcining prior to use of the catalyst iS Optional Regardless of Whether the catalytic con1position comprises uncalcined Dultic0mp0nent catalyst particles (Such as 0 -CHO Pt-A1 0 Of iS an uncalcined mixture of catalytic elements, the nal con1p0sition of the catalyst of tllis invention perf0fIns Substantially the Same, because nornlal 0 erating tenperatures of an aut0mobile exhaust converter are Sl1fficiently high t0 calcine the comp0nents In accordance vvith the pr0cess aspects Of the present invention, the automobile combustion exhaust gases of hydrocarbon fuels are 0xidized by contacting the eX- haust gases With a catalyst of this invention, 0f the type described above These hydr0carbon c0mbustion exhaust gases n0mally leave the combustion chan1ber Of n10st conventional internal conbustion engines, aS for example those empl0yed in auton0biles and trucks, at a temperature of from between about 300 to about 700 C; depending principally upon engine Speed In employing the catalyst of this invention and the process of this inventi0n, pellets are norInally introduced int0 a converter unit Which in turn nlay be inserted into the exhaust systen1 0f the internal c0mbustion engine (:0nverter" as that term iS emp10yed he1-ein refers t0 any Suitable container for the catalyst particles of this in- Vention Which preferably is capable of being inserted int0 the exhaust system of an internal c0mbustion engine, as for exanlple, before OT after or in liell of a mumer, after the exhaust rna1if01d or Other convenient 10cations such a converte1 preferably should be employed iIl the Systen1 in a region Where the ten1perature of the exhaust gases ()f fron1 between about 300 C' and about 72j C' In accordance With the present invention, such a converter iS preferably equipped Vith a nleans 0f insuring controlled air induction S0 that the ovv of air with the OW of exhaust gases as the time 0f contacting the 0xidation cata lyst is appr0ximately .05 to 3.0 cubic feet of air per n1inllte The Ovv rate should be such that it substantially maintains an 0 concentration of at least about 2) and below ab0tlt 66. 0xygen OT air OW Substantialy in excess of about 6-% 0 substantiany increases the incidence of c001ing of catalyst bed or alternatively of overheating, discussed above. The catalyst 0f this invention is novel in that, for exaInple, high OIein conversion iS obtained Vvithin these requirenents lhis air rate is such that Cat alySt temperatures Will reach bllt norfnally not exceed 72 C.

The J(ed controlled air rate to achieve a naxinun] catalyst temperature Of 725 iS dierent for different cars because of Such fact0fs aS engine Size and p0sition of the catalytic unit in the car Larger engines Will re quire more air `(/ith the catalytic unit at the rear of the car, Inore air Will be required than one having the unit nearer the exhaust nanif01d.

The enp10yment of c0ntr01led (Xed) air 0W is an imp0rtant part of this invention Since it can reSult in near constant and optinlum catalyst tenTperature That is, at low exhaust rate (idling and 10W Speed) vvhen carbon monoxide and hydrogen content are normauy high and exhaust telnperature is low (300400 the rati0 0f 0Xygen reacting to total gas is high for an active catalyst S0 that adiabatic heat rise is also high on the 0ther hand, at high Speeds when exhaust teI1perature iS high (00 60 and carbon mon0xide, hydrogen and hydrocar bons lovv, the rati0 0f total 0Xygen t0 total gas iS 10W S0 that adiabatic heat Tise iS 0vv. The net eifect is t0 [[laintain a Ilear constant ten1perature and Tealize optinlum per f0rnlance Inlet oxygen levels to the catalyst and gaS teInperatures at Xed air induction (2.0 c f'm.) vvill vary With engine speed in terms of miles per hour on a normal 6 cylinder car about as ill1strated in Table VII below.

*Readin on s eed01neter of iacked u car. 1)[. 'h' a roxinates clf n1. f eXhaus AS exeInplary 0f a suitable converter en]p10yable in the process of this invention, the converter il111strated in the accompanying dravving nlay be enp10yed in vvhich drawing;

FIGJR E 1 is a side elevation of said c0nverter;

FI(IJRE 2 is a top sectiona1 view along the line zz of FIGURE 1;

IGURE 3 is a vertical sectional view alon the line 33 0f FIGURE 1; and

I(JlE 4 iS a perspective View of the convertef.

This converter unit consists of a cylindrical housing 1 insulated by asbest0s 0l other Suitable insulating mateial 2 having an inlet 3 to its interior 4 and outlet 5 therefrom.

Catalyst penets 6 are placed in the interior 4 0f the convefter unit through opening 7 having a renVable cap 8 positioned thereover. catalyst pellets G are p0sitioned between vertically spaced parallel grid plates and 10 having unifor[n perforations therein 11. In 0rder t0 deteTnine accurate1y the ten1perature in various parts of the catalyst bed of the converter unit, thernOWellS 12 are positioned in the converter unit between grid plates 9 and 10 With exposed ends 13 S0 that temperature readings Within the catalyst bed are readily 0btainable.

The inlet pipe 3 and the outlet pipe 5 Inay be threaded (n0t Shown) 01 0therwise Suitably mechanica11y adapted for being Ten10vably p0sitioned into an exhaust Systen as, for example, at about a f00t's distance fron1 the exhaust n1anif01d In operation exhaust gases entering through in1et 3- at high ve10city are forced down through upper grid plate through the catalyst paIticles Xed through grid plate 10 and the 0Xidized gases exit through outlet Pipe 5 llltiIT1ate1y fOT transmission int0 the' atm0sphere In accordance With the present process, 0xygen, referably as air, is fed t0 the exhaust line or directly to the converter aS by means of a suitable venturi device 0r air pump not Shown Sllch devices are adaptabe to providing the anlount of air specified ab0ve,

In order that the present invention Inay be 'm0re fully understood, the fon0wing examples are given prin1arily by vay of i11ustration 1TO details or enumerations contained herein should be construed aS 1imitations Ol the present inventi0n, except ins0far aS they appear in the appended claims All parts and pefcentages are by vveight unless 0therwise designated.

Example 1 j 4 g Of Water and 481 g of ammoniun1 metavanadate aTe slurried t0gether in a Suitable mixing vessel and vvarmed With Inixing to S0 780 g Of 0Xalic acid are added slowly over a period of hour, oontr011ing the temperatuTe at from between S0 and 60 The Solution iS agitated until the evolution Of carbon dioxide has ceased and thereafter c001ed t() 2 vith the Slow addition of 173 g. 0f 28.1% amm0nia.

120 g 0f ganma a1[1frina prepared by the reaction between alllm and an alkali metal aluminate Which had been Spray dried and calcined for 1 hour at 700 F. Was added t0 a n1uller and the s0lution prepared above added theret0 and the II1ix mulled for one houl 'lhe Tesulting conlp0sition Was then extruded to ex trudates, dried overnight at 2S0 F. and calcined 01 one houl at 1100 1 Exa...mple 2 SZ S lbs Of alunina extrudates, the alunli11a of which vvas derived ffon1 alum and an alkali metal aluninate vvere impregnated by !Tll11tipe impregnations at 80-100 with S0lutions 0f an1monia Inetavanadate and water to yied a inal product which contained 13% 0 0n a calcined basis. The catalyst is il111stfated in Tables )(I, and (II. Additionally, a catayst of the same general type is illustrated in Table )(V.

Example 3 Gamma alumina, made fr0:m a sol according to U'S. Patent 2,Z74,434 vvas impregnated vvith an aqueous Solution of ch10r0platinic acid and aluIninum ch10ride hexahydrate to yield a product upon drying and calcination at 1100 F which contained 0.3% laltinun and 1.1% ch10ride` Example 4 One hundred graIns 0f alumina extrudates vvere impregnated with a soluti011 0f CI1(NO '3H 0 and water (33.6 gm. CH(NO '3H 0 diluted to 75 cc. with water)( The alumina extrudates Were titrated vvith the cupric nitrate solution t0 a pore volume end 0int' The resulting catalyst was then dried overnight at 2S0 F and calcined one hour at 1100 F.

9-9 grams (l cc.) Of the above catalyst containing 10% Of Cu0 Was physicany admixed With 20'z grams (3S cc.) of V O Al O containing 13% V 0 The over-all catalyst contained 3% CuO about 9 V 0 and the balance alumina.

Example j Fifteen pounds of silica Stabilized (2% Si0 alun1ina in bead forIn were ilnpregnated with amrnoniun1 Inetavanadate After impTegnat0l the Inaterial vvas dried at 2SO F, for 70 hours. ()n ana1yzing, the Inaterial vvaS Shovvn to contain 10.4%

16.58 ounds of the above naterial Were impregnated vvith 3230 cc' Of a vvater solution contai11ing 1)Z7 grams of panadiun1 ch10ride S0 aS to Saturate the pores. The impregnated n1ateria1 was dried overnight at 20 F. and subsequently calcined one hour at 1100 F. 'lhe nal product contained 10.4% V 0 0.01% pauadiun1, and 1.8% Sio On Al 0 Example 6 Catalyst containing l 0% V 0 and parts per nillion palladium repared as described in Example S Was impregnated vith copper Ilitrate solution by the pore Saturation method using 65 g. 0f Example 5 catalyst and 39 cc 0f a copper nitrate Solution containing 10.3 g. 0f

l`he Saturated catalyst was dried overnight at 250 l and calcined for one hour at 1100 F. yielding a product containing: 10%) V 0 4%) copper oxide and 100 )arts per million 0f palladium.

Exam le 7 Sixty four pounds of Silica stabiliZd alumina (2% Si() in the form of beads were mpTegnated vvith ammonium nTetavanadate to give a final product which contained 10% v 0 after drying at 250 F.

Twenty two pounds of the dried 0 1 vvere impregnated with 4610 cc. of a vvater solution containing 937 g 0f C11(NO '3H O and 1.7 g Of auadium chl0- Tide so as to Saturate the pores The mpregnated n1aterial vaS dried overnight at 2jo 1 and calcined f01 two hour at 1100 F. so aS to give a Iinal product containing I10% V20 100 parts pel mimon panadium and 3% copp01 0xide.

Example 8 (atalySt containing 11% 20 and 100 parts per million of palladiun1 prepared as desuribed in Example 7 Was impfegnated vvith copper nitra'e Solutin by the p0re Satufati0n method using 70 g. Of Xafnple 7 Catalyst and 39 cc. 0f copper nitrate solution containing 23.6 g. CU(NO '3H 0 in Water The satutited material Was dried for 70 hours at 2j0 F. and one hour at 1100 F., S0 aS t0 give a pr0duct c0ntaining 10 100 paTts per million palladium and c0ppe 0xide Example 9 Exanple catalyst (7 7 pounds) used in a catalytic TABLE vIILCOMPRISON OF EFFEOTS OF OATALYST TYPES ON EXHAUST GAS n In1et Inlet Tem er- Percent A B C D E F ature, 02

l0tal I ercent IIC Roll10v0(1 Exclusive OI 400 79 Methane, b 400 6 81 400 8 83 320 44 Percent H2 0xidized 400 3' 5 8 l ecent C0 0xidized 400 3. 5 5

zt On treat1nent 0f exhaust fl'on1 Lauson 6`3 I'1 engine, Teferred to above( Con1positi01: 6.9% C0, 3.6% H 2 0-5% EC'S CH4, C2H2, 30% C2H4, 20% O3 N2 and Ar on b Methane considered harn1less and therefore subtracted out f1-om tota1 values' Air added t0 exhaust ases before inlet to catal st to rovide ox cn love1 indicated l'Iller on a 1950 I I[1Clson With leaded gas01ine for 1100 n1iles Was ifnpregnated With 1840 cc copper nitrate SO lution containing 328 g. 0f CU(NO '3H 0 SO as to Saturate the pores and give a product containing 3% (;ll0 The saturated roduct was dfied at ZSO F. and calcined for one hour at 1100 F.

Example 10 200 g of gamma alumina (Silica stabilized, 2% sio vvere impregnated with a Slurfy of an)monium metavanadate The impregnated material Was dfied at 2j0 for 48 hours and a portion Subsequently calcined for one hour at 1100 F. TT1iS material contained S'6) V 0 162 g' Of the above material dried at 250 F' Were ilnpregnated S0 as to saturate the pores vvith 90(7 cc. 0f a water solution containing 2S 8S g of and .0267 g. 0f panadium chloride The above -rnaterial WaS dried for 17 hours at ZSO F and Subsequent1y calcined for one hour at 1100 F. The iinal catalyst contained j% c0pper 0Xide, 0 01% Of palladium, j 3% Of V 0 and 1.8% Sio On A 0 A Series of catalysts, AF identified hereinafter in 1`able IX and prepared generany in accordance VVith the rocedure Set forth in Examples 2-4 and 7, 8 and 10 Were tested to determine their eect on the exhaust gases frorn a 6 3 horsepower Iauson internal combustion en gine, refefred to above as producing about 80% 01efins of Which about 63% Of t0tal olefins are olefins of three or Inore carbons The results are Set f0rth in Table VIII below,

The test unit empl0yed in obtaining the teSt results illustrated in Table VIII Was designed primarny to obtain information on eect of variables rather than to du licate exactly a catalytic mumer It COISists of fouf 1 inch dian]- etel tubes which it c10se]y inside holes in an aluminuIn bronze block Catalyst (S0 cc-) iS charged to the central Zone Of these tubes EXhaust fronl a Iauson 6-3 II'P engine is joined by an air Strealn before passing through the catalytic bed in tests on exhaust gas (...aS Samples ale taken bef0re and after the catalyst to deternine eect of catalyst and analyzed by ame ionizati0n for hydr0- carbon content, by heat evaluation 0n pasSage through hopcalite for carbon Inon0xide and by thermal conductivity for hydrogenvvhen the unit is operated at about 320 C inlet and b10ck tenperature, there iS Substantial (l00200 C() temperature rise when 0Ve1 half the hy- The compos...0n Values of AF inclu8ive Of Table VIII are iuustrated in Table IX.

TABLE IX San1ple NuInbor Exam le C0Tn onents, ercent Number It is apparent ffom Table VIII that the platinum catalyst (B) is t00 active for carbon monoxide and hy drogen reduction t0 be very effective for hydr0carbon 0Xidation, unless very high 0Xygen levels ae emp10yed (6% and 8)), Which requires high air induction rate and causes overheating of the catalyst in an adiabatic llnit. The low activity 0f the 0 -AI O catalyst (A) at 10W ten1perature for hydr0carbons is als0 appafent aS is its 10W activity for hydrogen and carbon mon0xide Although it vvill be observed that catalysts D, E, and F, typical catalysts of this invention, are less effective than catalyst A and as or more than B, in conversion of hydrocarbons at 0Xygen levels of about 4% nevertheless, Catalysts D, E, and F, are advantage0us from the 0int of view of 10Wer C0St, faster Varmup time and better Stability, and are more attractive than Cataly8t A and broadly better than B for the reduction of carbon mon0xide, hydrogen and hydr0carb0ns In order to attest the eectiVeneSS Of catalysts A-F, identied hereinabove, On pure hydr0cafbon exhaust gaS feeds and in particular their effectiveness vvith respect t0 ethene (i.e ethylene) and propene (i'e propylene), comparative tests were made on these materials at tem- Peratures 0f 400 and 320 Tespectively The results of this c0mparison are Shown in Table X hereinbe10w.

TABLE X'TESTS ON PURE HYDB0CARBONS "Mu1ti 1etestunit, Tnin. 0f 1% (m01 ercent c in air Table x above establishes that catalyst Of this invention (C, D and 1 are clearly ITOre eifective for olefin 0Xidation than catay5t A, the V 0 catalyst (employed alone High surface area alunlina Spheres (Alcoa H1j1) is 2 recycle Of spent Solutin Batch n1akeup quantities are gVen bel0V.

*Union Garbide C0'-T eTechnica1- rade cata1yst.

impregnated vvith a S0lltion of urany1 Ilitrate, copper nitrate and chromium nitrate vvater is removed on a Steam bath and the p10duct is igl1ited in ail` at 700 C. in a mue A catalyst Of thiS general type is illt1strated in Table XIII` Example 24(PHZ3.l)

A catalyst Of the type prepared by the Bureau 0f I/IiIles, containing about 2.j% Cu0 and about S 8% Cr 0 is illustfated in Table )(III Example 2(4473132) An alumina base catalyst containing about Fe 0 (aS repared A catalyst of this nature is illustrated in Table XIV.

Example 26'(4633l4j) 1263 g of alumina base Was pore Saturated vvith 92-2 cc Of j0.2% Mn (I1I() .6WII 0 S0111tion The in1pregnated n1atefial vvas dried for 18 hours at 250 F and ca1cined for l hour at 1100 F.

Example 27 (4473l3 1) AT alunlina base catalyst containing about Cr 0 Was prepared A catalyst of this Ilatllfe iS il111strated in Table XIV Example 28 (NB 4633107) A catalyst similar t0 that Of Example 11 Was prepared, except that the nal catalyst contained about 10% C110. A catalyst Of this type iS ill[1strated in Table )(IV' Exam le 29. NB 463373 100 g Of base (j134lj) is pore Saturated With 84'3 cc of a Solution containing 0.602 g. Pd as Pdcl and 2 2S g' ACl '6I-I The catalyst is dried for 18 hours at 250 F' and calcined at 1100 F for l hour A catalyst of this general type is illustrated in Table IV, the Pd content being about (),-6%

Exam le 30 4999I5 Exam le 31 An extrudate catayst having a ffesh bulk density of 0,64 g'/cc', c0ntaining about 5-3% V 0 6,4% Cu0, 0-01% Pd, and Si0 is illustrated in Table XV. This catalyst WaS prepared at a major catalyst production facility jy the typica1 OIl0wing procedures (1) /anadiun1 impregnation.Three batches of Sized calcined beads Were impregnated 3 hours at 180 F with The Tesulting ilnpregnated beads Were drained of free Water and transferred to a belt dfier vvhere the v0latile Content Was Teduced to about 9'%)- (2) C0pperpa11adium impregnation.This impregnation WaS canied out iIl a rotating druIn impregnator. Five batches having 275 1b. of dried vanadized beads in each batch, Were each impregnated With 210 lb (21 gal 0f lution containing S7 lb- CU(No .3H 0, 10 lb water at 130 F and 1200 CC- (2 b.) 0f Solution containing 20-3 g Of 60% Pd palladium ch10ride and 30 cc conc HC]. The S01llti0n WaS Sprayed Via 16 nozzles in lS IIlinutes. All )atcheS appeared uniforn1]y Wetted, I10t t00 Sticky for g00d 0W.

(3) ]rying, calcination and nal screening.wet beads Were dried and calcined in an indirect fred kiln The kiln was run With a product temperature range of 1150 IZOO at about 200 1'b./hr' feed (D B').

Example 32.(4473-89 and 633103) A catalyst of the type having a fresh bulk density 0f 0-64 and containing abollt 11% Cuo is illustrated in 1able V. The catalyst iS Of the general type prepared in Example ll( Example 33.(jl39l0ll through 6) Seven hundred and fty grams of beads (4994761, 2, 3 and 4) at Si0 -9S% Al 0 Was slurried With 77 grams of NH V0 The Slurry Was held at a b0il for S hours The beads Were Separated fron1 the liquid and ovendried for 17 hours at 2S0 F. The beads were ore Saturated With a S0]ution containing CU(N0 and PdC I'he copper and palladia concentration Were adjusted S0 that the HIlal catalyst c0mp0sition Would be 2 Cuo and p p m. Pd' The Wet beads were dried at Z0 F( for 18 hours and calcined for 1 hour at 1100 F The finished Catalyst was screened into a Size range Of Tyler mesh, size 6-8.

A catalyst Was prepared by the procedure described in Example 33, except that this catalyst vvaS Of a Tyler Inesh size 10 to 12,

Example 3,(134-1012) A catalyst Was prepared by the pr0cedure described in Exan1ple 33, except that this catalyst Was of a Tyler Inesh Size Of14to16 Examples 36 through 43 are i11ustrated in Table XVII` Except for the variations in the nature and percentage of stabilizer en1p10yed, each of the cata1ystcon1p0sition8 Were prepared by a pr0cedure which iS typically Tepresented by the following procedure In each example, the spraydried materal Was admixed with water and extruded t0 yield a base which Was subsequently impregnated With catalytic agents t0 0btain the fl!lal catalyst 20 g. 0f extrudates are Slurried in a basket with 2.6 g. 1II V() This basket is 10Wered into a beaker containing 600 cc. 0f Water and b0iled for about hour The ma- AS discussed above, the ability Of a catalyst t convert olef...ns of three Or Inore carbons iS a fact0r of nTaj0r imortance in the Control of Srnog conditions Similarly, an- 0ther n1ajor factor is the ability of an automobile exhaust catayst to become effective for purposes of conversion at a low temperature, i.e, it iS i111100rtant for the catalyst t0 have a W ignition temperature A Con1parison 0f EX- amples 11 through 18 bear on these factors A con1parison Of the ignition temperatures of Examples 11 12, l3, 14, and 18 discloses conparative ignition ten1peratures of 23Z6 C, 290 C 18S C 306 C 204-20 C, and 2d8 Tespectively In a considerati0n of ignition ten] erature aS a Single factor, independent of the many 0ther important factors ass0ciated With an aut0mobile exhaust conversion catalyst, These examples ilIuStrae that the ignition teInperature of applicant,8 C0Inposition aS illustrated in Example 18 is Signicanty 10Wer than the ignition temperature for particular Sngle cataySS enloyed alone, Such as latinum, Which haS an ignition ternperature of 290 and that appicant,S C0mp0sition has aS g00d an ignition temperature (240Z0 C) aS C0pper e[np10yed alone 23S26j C`) A c0mpari80n of the ig nition temperatures further discl0ses that applicant's C0Inp0sition of Example 18 iS Superior t0 the random combination illust1-ated by Example 14, Which employs c0pper, pa1ladil]m, and platinun1, and Which has an ignition tenperature 0f 306 C- The fandom catalyst C0Inbination ill[1strated by Exa111ple 14 Substantiates that there is no apparent reason t0 expect a COInbination of Several catalysts t0 0btain a 10W ignition tenperature. This iS particularly true in the light of the fact that the ignition tel11 )erature resuling from the combination of coppe, alladiu1 and )latinuIn, is 306 Which iS Substantially higher than the ignition temperature 0f any one 0f the cataly81s employed alone, Such as CO per2326S C, 0r 1latinum 290 C', Or panadium185 C Continuing the C0Inpafison, Exan1ple 1 illustrates that panadium employed alone as a catayst obtained 97% carbon mon0xide conversi0n but obtained merely a low 62% conversion of t0tal hydrocarbons( v-'hen ernp10ying such a' catalyst in an aut0mobile exhaust convef[er, in order t0 obtain a Satisfactory t0tal hydr0carbon conver- Sion, it would be neceSSary t0 alSo emp10y an air or oxygen c0ncentration in Such high an]0unts that the 0Verheating pT0blem Would be encountered Example 16 en1- loying palladiun1 and platinun1, and illustrative of a rand0m 1T]ixture 0f catalysts, encounters the identica1 problem, 0btaining a high carbon n]0n0xide conversion Of 96 Vhile obtaining a t0tal hydr0carbon conversion Which may reach a nere 68'%)- Exarnples 11 and 17 en1p]0ying copper alone in ercentages of 11% and 1Z), When c0mpared to the inventive C0mpositi0n 0f Example 18 employing 7% vanadia, j% co er, and 0 01% alladium, as Well as the con1parison Of the inventive con1position illustrated in Example 18 as compared to the foreg0ing EX- a[nples 1 and 16 Substantiates the Superiority Of the in- Ventive c0mp0sition in obtaining a high percentage conversion Of total hydr0carbons, Carbon mon0xide, and C H typica1 Of OlenS Of three or n10re carbon at011s. The table d6Inonstrates that the inventive comp0sition 0f Exan1ple 18 0btains 98% conversion of C H aS contrasted t0 copper emp10yed alone Which obtains n1erely 88% conversion 0f C II The 90% Of total hydr0carbons of the inventive c0mp0sition and the 100% carbon m0- 110Xide conversi0n of the inventive comp0siti0n are in contrast to Examples 1S, 16 and 17 Which fail t0 0btain a high percentage 0f conversi0n of total hydrocarbons c0ncurrent With obtaining a high percentage conversion of carbon In0n0xide.

Thus, fr()m Exan]ples 1 1 through 18 it iS apparent that all compositions of random catalytic IT1aterials do n0t necessarily improve igniti()n ten1 )erature; f0r example, the ignition temperature 0f the rand0In Catalyst of EX- ample 4 Was Sig1ificandy higher than he ignition ten perature obtained by any one Of the caalyStS en] )I0yed a10ne. It iS also conclusively shown that C0np0sitions of random catalytic Inateria]s do n0t necessariy improve the percentage conversion; for instance, ExaInple l6, Which employed palladium and platinunl in con1bination, failed t0 0btain a high percentage 0f conversion 0f total hydr0- carbons and Similarly, copper eInp10yed alone in ExaInples 11 and 17 failed to obtain a high percentage conversion of total hydrocarbons ol 0f ropylene H in contrast to the inventive composition of Example 18, Which obtained a high percentage conversion in all Of these aleas The foreg0ing eXanpleS als0 illustrate that a catalytic c0mposition emp10ying random mixture8, Such as EX- afnple 16, may be satisfactory When considered f0r a Single Propefty, Such aS ignition temperatures, for use in an aut0mobile exhaust cOnVeter, but iS not Satisfact0fy for obtaining the high conversi0n Of b0th t0tal hydfocarbons and carbon monoxide, for instance; Example 16 is illustrative ()f this point having a 10W ignition tenperature Of 221 C but obtaining an unsatisfact0ry percentage conversion of total hydrocarbons, 0btaining a nere 58% aS contrasted t() the inventive C()mPOSitOn (Exafnple 18) Which obtains In contrast to the 0ther examples, Example 18 Which illustrates an embodiment Of applicant's invention discl0ses that the inventive con1p0sition obtains the deSiled 10W ignition teInperatufe, a high degree of conversion of 0lefins having at least three carbon at0ms, a high degree 0f conversion of total hydf0carb0ns, and a high degree Of conversion of caTbon n1on0xide EXam eS 19, 20, 2l, 22 Z3, and 24 illustrate the con1- parative resistance t0 leading desensitization Of C0mp0- Sitions (Exanples 20 and 22) Which are typical embodiments of applicant's invention, in contrast to Single cata lysts en]p10yed alone (Example 19 and Example 21), and catalysts representing random C()IT1bination of catalytic materials (Example 23 and Example 24), A c0mparison of elnbodi...nents of the inventive c0mp0sition of Examples 20 and ZZ illtlstrates the Superiority of the catalyst Comp0- Sition of this invention to rand0m catalytic agents used alone Or in c0mbination, Such aS Example 21 elT1p10ying pauadium alone, Example 19 en1p10ying vanadia alone, and ExaInples 23 and 24 emp10ying Various c0mbinations of copper 0Xide, urania, and chromium oxide The com- 0Sitions of this invention, ie Examples 20 and 22, demonstrate a high degree Of fesistance t0 lead p0isoning, retaining 90 j% and 83% Conversion activity for total hyd[0carbons, respective1y, and retaining Conver- Sion activity for carb0n mon0xide for each Tespectively' The high degree Of resistance to lead p0isoning of the in ventive efnbodiments il11strated in Exarnples 20 and 22 iS in contrast t0 the oor Tesistance to lead )0is01ing defnonstrated by Examples 21 '(paladiuIn alone), 23 (copper oxide, urania, and chr0mium 0xide), and 24 (copper 0xide and chr0miuIn 0xide) Exan1ples 19 through 24 inclusive 0f the above Table III iS evidence Of the clearly supefior pr0perties, i.e., pefcent conversion of emb0diments 0f the catalyst Of this invention after leading, and that Such Superior characteristics could not have been )redicted from a consideration of the pr0perties of each of the c0mponents alone. Additionally, Examples 20 and 22 illustrate the exception ally good resistance to leading of the catalysts of this invention as compared, for exaInple, to a cop er 0Xide- Chr0Inium 0Xide catalyst, aS Tepresentative of a random con1bination con1position Table XIII further inustrates Examples 2, 4, 7, 8, 10, and 11 den10nstrating the Superi0fity of various embodiments of applicant's con}positi0n (Examples 4, 7, 8, and 10), aS c0ntrasted t0 vanadia alone (ExaInple 2) and copper alone (Example 11), in regard t0 the ability of an aut0mobile exhaust gas catalyst t() convert Olens having at leaSt three carbon at0Ins, Such as pf0pylene (C H "Ignition temperature," as defined and discussed above, felates t0 the ten1perature at Which an aut01110bile exhaust Table xIX inustrating Examples 44 and 4 demon- Strates the effect Of pore vlume 01 lead tolefance and on crush strength for two Separate embodiments of applicant's invention. The two Examples 44 and 4j are Sub- Stantially Similar except fol the dierenCe in pore volume The table discses that the loss of catalytic activity for the conversion of hydr0carb0ns upon`being leaded vvas a loss of 10% for a ore volume of 0 7j and a 10ss of about 22% for a p0re volume 0f 060. Thus.^it is seen that the Sensitivity 0f the catalytic comp0sition t0 leading Substantia11y increases as pore v0luIne decreases Table (I)( additiona11y disc10ses, however, that aS the pore volume decreases from 0 74 to 0.60, the crush Strength, as reected by the number of iines produced by 400 pounds pressure and by iet attrition, approximately doubled, ie the number of Iines produced in Example 4 catalyst Were appr0ximate1y 0f those produced by ExaJnple 44 catalyst 0ther suitable changes and variati0ns may be nlade in Carrying out the invention as described herein vvithout departing ffom the spirit and scope there0f, as deHned in the appended claims.

1. A process for oxidizing exhaust gases fr0m hydr0 carbon fuels comprising contacting said gases with an exhaust gas converter catalyst in the I)rSence of at least about 2% to about 6% ox en, Said catal st com risin a n1ajor portion of alumina between from about 2% to about 10) Of vanadia, and between froIn about 2% t0 about 10% Of copper, Said percentages being by vveight 2- A process for 0Xidizing exhaust gases from hydrocarbon flels according to claim 1 in Which Said vanadia Tanges between fr0In about 4% to about 7%, in vvhich Said copper ranges betyveen froIn about 32 t0 about 7% in the forIn of copper oxide, and said catalyst additionally comprising between fronl about 0.01% to about 0 0lj% Of panadiun1, and silica in an amount sllcient to stabiize.

3 A Process according t( Claim z, in vvhich Said cata Iyst has a cr0ss Section of between fr0m about 0 0S inch t0 about o inch and has a pore volune of between from about 0.7 cc./g to about o 9 cc /g.

4. A process for 0Xidizing exhaust gases fr0n hydr0- carbon fuels according to claim l, Said pr0cess additionany c0mprising providing Said oxygen by OWing air at a rate 0f from between about 0.5 t0 about 3.0 cubic feet of ail per Ininute.

S A pr0cess for oxidizing exhaust gases from hydrocarbon fuels according to claiIn l, said( process addition ally C0mprising H0Wing said oxygen at a rate sumciendy high to substantially oxidize said exhaust gases, at a fate Suicienty 10W T0 Substantia1y prevent overheating of an exhaust gas converter, and at a rate Suciently low to substantia1ly prevent c00ing of said catalyst below the ignition temperature of said catalyst 6. An aut0m0bne exhaust gas converter including a bed of partic1es in1pregnated With oxidation catalytic Inaterial C0Inprising between from ab0u 4% to about 7%) Of vanadia, between ffonl about 3% to about 7) 0f copper in the fotn1 0f copper oxide, and between fron1 about 0.01 m about 0.015% Of palladiun said percent' ages being by Weight, Said particles havng a cross section betvvee11 from about 0-05 inch t0 about 0.20 inch, and a pore volume between ffom about 07 cc'/g. to about 0.9 cc /g.

7. In an auton0bile exhaust gas c@nverter according t0 clailn an 0Xidation catalySt-bed in Which Said particles include silica in an amount suflcient to stabilize said catalyst.

UNITED STATES PATENTS 2,942,933 6/l960 Batchelder et a' 232 3,04,422 7/1962 Houdry 23--2 3,ZZ4,981 1Z/196S Stephens et al 232 x U S. C1. x.R.

Patent No UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTION Dated APri1 5, 9 9

Wi11iam Beve rid e nne s t is certified that error a ears in the ab0veidentified atent and that said Letters Patent are hereb corrected as Shown be1ow:

1ine

1ine

1ine

1ine

line

Si ned and (SEAL) Attest:

EDWARD M.F'TETCHER,JR. Aesin Officer for for

for

for

for

"XVI" read Xv "Table XV" read Tab1e xv 1, for "Xx" read XV 2, for "XIX" read Xv sea1ed hi3 15th da of Februar 1972.

ROBERT GOTTSCHALK Commissioner of Patenbs 

